Mechanical-chemical energy storage

ABSTRACT

This invention generally relates to mechanical-chemical energy storage. In particular, the invention relates to a mechanical-chemical energy storage system that stores energy by simultaneously compressing a gas to a higher enthalpy state and recovering the heat of compression by driving a somewhat reversible chemical reaction. The heat energy in the chemical reaction is then recovered while the gas is expanding to a lower enthalpy state.

CROSS REFERENCE TO RELATED APPLICATION

This application is a divisional of U.S. application Ser. No. 14/329,201, filed on Jul. 11, 2014 and claims the benefit of U.S. Provisional Application No. 61/844,914, filed on Jul. 11, 2013, and 61/968,450, filed on Mar. 21, 2014. Each of these documents is incorporated herein in its entirety.

FIELD OF THE INVENTION

This invention generally relates to mechanical-chemical energy storage. In particular, the invention relates to a mechanical-chemical energy storage system that stores energy by simultaneously compressing a gas to a higher enthalpy state and recovering the heat of compression by driving a somewhat reversible chemical reaction. The heat energy in the chemical reaction is then recovered while the gas is expanding to a lower enthalpy state.

BACKGROUND

Energy storage is vitally important for the stability of the electric grid as it relies more on “non-dispatchable” sources of power such as solar and wind. Additionally, there are many applications where long term power may be needed apart from any grid such as in military or emergency situations. Currently, the most common solutions are lead-acid batteries and diesel generators. The shortcomings of these systems are well known. Most electrochemical batteries show a significant degradation in performance as they are discharged. This is evidenced by reduced voltage output and reduced maximum currents observed during the discharge of the battery. Batteries also tend to be less efficient and have reduced service lives when run at greater depths of discharge.

There is increased interest in using stored mechanical energy to ultimately serve as electrical energy storage for grid type applications. This interest is based in part on the robust nature and highly developed state of the art of mechanical power generation equipment, which is economical and scalable. In general, most energy storage schemes compress a working fluid to high pressures or liquefy the working fluid by compression and/or temperature reduction. Alternately, a series of heat pumps (often coupled to generators and/or other heat sources) indirectly accomplish this same goal where working fluid(s) is/are cycled with the combination of heat pumps. This alternative has higher cost associated with extra machinery. In general, to get higher recoveries (efficiencies that we will refer to as “round trip efficiency” or “RTE”) requires more “stages” to recover energy, and each additional stage is met with reduced energy recovery. Thus, these systems require increased capital to achieve high RTE after more than two stages.

Other conventional energy storage systems store energy by compressing a gas to high pressure. Depending on the physical properties (critical temperature) of the gas, it may liquefy. During this compression process, heat is generated and much of this heat is generally lost, which results in reduced RTEs. This is a common problem in compressed air energy storage (CAES). The RTE of conventional systems is around 50%. RTEs of these systems are limited due to the use of assisting gas turbines during operation to increase the overall efficiency of that device. Assisting gas turbines are not a true energy storage systems, but act as a hybrid, wherein stored energy is only recovered if it is also desired to burn natural gas to run the gas turbine to create energy.

Traditional efforts to recover this heat from compression involve storing the heat of compression in a medium (such as water), as sensible heat, which simply raises the temperature of the water. This warm water is stored in an insulated tank until the energy is required to heat the working fluid while expanding it to recover that energy. However, warm water has reduced energy dense medium. Furthermore, the low temperature gradients present engineering challenges to achieve high power output that requires high rates of heat transfer over a low temperature gradient. Problems also exist due to heat from the stored water escaping from the insulated tank giving the system an apparent “self-discharge”, analogous to electrochemical batteries.

SUMMARY OF THE INVENTION

The present invention solves one or more of the problems described above by combining the high energy density of a liquefied gas, the high RTE of operating near ambient temperatures, and the ability to achieve high power densities by generating the heat required for expansion when it is needed rather than storing heat for use at some other time.

In one aspect, the present invention provides a method for storing energy comprising: providing an absorbent reservoir containing a working fluid that is chemically absorbed by an absorbent; desorbing the working fluid from the absorbent in an endothermic process; and condensing the working fluid in an exothermic process and transferring the condensed working fluid to a working fluid reservoir under pressure, wherein at least some of the heat generated during the condensing step is recycled to drive the desorbing step.

Another aspect of the present invention provides a method for storing energy comprising providing an absorbent reservoir containing a working fluid that is chemically absorbed by an absorbent; desorbing the working fluid from the absorbent in an endothermic process; and condensing the working fluid in an exothermic process and transferring the condensed working fluid to a working fluid reservoir under pressure; wherein at least some of the heat generated during the condensing step is recycled to drive the desorbing step.

In some implementations, the working fluid comprises carbon dioxide, ammonia, nitrous oxide, air, or water. For example, the working fluid comprises carbon dioxide or ammonia. In some instances, the working fluid comprises ammonia. In other instances, the working fluid comprises nitrous oxide.

In some implementations, the absorbent comprises an organic amine, an inorganic base, an activated carbon, silica gel, a zeolite, a metal organic framework, or any combination thereof. For example, the absorbent comprises an organic amine selected from monoethanolamine, piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, diethylenetriamine, or any combination thereof. In other examples, the absorbent comprises a metal halide salt, a mild acid, water, activated carbon, silica gel, a zeolite, or metal organic framework. And, in some examples, the absorbent comprises a food oil, silicone oil, activated carbon, silica gel, zeolite, or metal organic framework.

In some implementations, the heat generated from the condensing step is recycled to drive the desorbing step using a heat exchanger.

Some implementations further comprise compressing the working fluid using a reversible turbine.

Some implementations further comprise compressing the working fluid and storing the working fluid in the working fluid reservoir in a liquid state, a critical state, or a trans-critical state.

In some implementations, the working fluid is compressed to and stored at a pressure of from about 1 bar to about 100 bar.

Some implementations further comprise a second compression step after the first compression.

In some implementations, the working fluid is expanded to a pressure of from about 0.1 bar to 10 bar.

In some implementations, the working fluid is stored at ambient temperature.

Some implementations further comprise heating the working fluid prior to expansion using an external heat source.

Another aspect of the present invention provides a method of charging and discharging an energy storage system comprising charging the system comprising providing an absorbent storage tank containing a working fluid that is chemically absorbed by an absorbent; desorbing the working fluid from the absorbent in an endothermic process; condensing the working fluid in an exothermic process and transferring the condensed working fluid to a working fluid reservoir under pressure; recycling heat generated during the condensing step to drive the desorbing step; and storing the working fluid in a working fluid reservoir under pressure; and discharging the system comprising expanding the working fluid; chemically absorbing the working fluid with the absorbent in the absorbent reservoir in an exothermic process; recycling heat generated during the absorption reaction to drive the expanding step; and storing the absorbent and the absorbed working fluid in the absorbent reservoir.

In some implementations, the working fluid comprises carbon dioxide, ammonia, nitrous oxide, air, or water. For example, the working fluid comprises carbon dioxide. In another example, the working fluid comprises ammonia. And, in some examples, the working fluid comprises nitrous oxide.

In some implementations, the absorbent comprises an organic amine, inorganic base, activated carbon, silica gel, zeolite, or metal organic framework. For example, the absorbent comprises an organic amine selected from monoethanolamine, piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, or diethylenetriamine. In some examples, the absorbent comprises a metal halide salt, mild acid, water, activated carbon, silica gel, zeolite, or metal organic framework. And, in some examples, the absorbent comprises a food oil, silicone oil, activated carbon, silica gel, zeolite, or metal organic framework.

In some implementations, the heat generated during the condensing step is recycled drive the desorbing step using a heat exchanger.

In other implementations, the working fluid is compressed by a reversible turbine.

Some implementations further comprise compressing the working fluid and storing the working fluid in the working fluid reservoir in a liquid state, a critical state, or a trans-critical state.

In some implementations, the working fluid is compressed to and stored at a pressure of from about 1 bar to about 100 bar.

In other implementations, the compressing step comprises a two-stage compression process.

In some implementations, the working fluid is expanded to a pressure of from about 0.1 bar to 10 bar.

In other implementations, the working fluid is stored at ambient temperature.

Some implementations further comprise heating the working fluid prior to expansion using an external heat source.

Some implementations further comprise directing the flow of the working fluid a first direction during charging, and reversing the flow of the direction of the working fluid during discharging.

Another aspect of the present invention provides an energy storage system comprising a working fluid reservoir containing compressed working fluid; an expander that fluidly communicates with the working fluid reservoir and is configured to expand the working fluid; an absorbent storage reservoir containing an absorbent, wherein the absorbent reservoir fluidly communicates with the expander and is configured to receive and absorb the expanded working fluid; a first heat exchanger that thermally communicates with the absorbent reservoir and is configured to transfer heat generated by the absorption of the working fluid by the absorbent to the working fluid during the discharge of the system; a pressure release mechanism configured to reduce pressure in the absorbent reservoir; and a compressor that fluidly communicates with the absorbent reservoir and fluidly communicates with the working fluid reservoir and is configured to compress the working fluid that desorbs from the absorbent; and a second heat exchanger in thermal communication with the working fluid in the compressor, in thermal communication with the absorbent and working fluid in the absorbent storage tank, and configured to transfer heat that is generated by the compression of the working fluid, to the absorbent and working fluid in the absorbent storage tank.

In some embodiments, the working fluid comprises carbon dioxide, ammonia, nitrous oxide, air, or water.

In some embodiments, the absorbent comprises an organic amine, inorganic base, activated carbon, silica gel, zeolite, or metal organic framework. For example, the absorbent comprises an organic amine selected from monoethanolamine, piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, or diethylenetriamine. In other examples, the absorbent comprises a metal halide salt, mild acid, water, activated carbon, silica gel, zeolite, or metal organic framework. And, in some examples, the absorbent comprises a food oil, silicone oil, activated carbon, silica gel, zeolite, or metal organic framework.

In some embodiments, the compressor and expander comprise a reversible turbine.

In other embodiments, the compressor comprises a turbine, piston, radial reaction turbine.

In some embodiments, the expander comprises a turbine, piston, or turbo-expander.

Some embodiments further comprise an electrical generator connected to the expander.

Some embodiments further comprise a motor connected to the compressor.

Some embodiments further comprise an external heat source, in thermal communication with the expanded working fluid.

Some embodiments further comprising a controller connected to the compressor, expander, pressure release mechanism, absorbent storage tank, and working fluid storage tank.

In some embodiments, the first heat exchanger and second heat exchanger each comprise high surface area fin-shaped structures within the absorbent storage tank.

Some embodiments further comprise one or more additional compressors, fluidly connected to and positioned between the first compressor and the working fluid storage tank.

Some embodiments further comprise one or more additional expanders, fluidly connected to and positioned between the first expander and the absorbent storage tank.

In some embodiments, the pressure release mechanism is a valve.

Some embodiments further comprise a pump and a sprayer that each fluidly communicates with each other and with the absorbent storage tank, wherein the pump pumps the absorbent and absorbed working fluid to the sprayer and the sprayer sprays the fluid back into the absorbent storage tank. For example, the sprayer sprays the absorbent over a heat exchanger with high surface area fin-shaped structures within the absorbent storage tank.

Some embodiments further comprise a separator that fluidly communicates with the absorbent storage tank and the compressor.

In some embodiments, the separator is a centrifugal or cyclonic separator.

In some embodiments, the separator is a demister or a tilter.

Another aspect of the invention provides a method of charging and discharging an energy storage system comprising: (i) charging the system comprising: providing an absorbent tank containing a working fluid that is chemically absorbed by an absorbent; desorbing the working fluid from the absorbent in an endothermic process; condensing the working fluid in an exothermic process and transferring the condensed working fluid to a working fluid reservoir under pressure; recycling heat generated during the condensing step to drive the desorbing step; and storing the working fluid in a working fluid reservoir under pressure; and (ii) discharging the system comprising: expanding the working fluid; chemically absorbing the working fluid with the absorbent in the absorbent reservoir in an exothermic process; recycling heat generated during the absorption reaction to drive the expanding step; and storing the absorbent and the absorbed working fluid in the absorbent reservoir.

Another aspect of the invention provides an energy storage system comprising: a working fluid reservoir containing compressed working fluid; an expander that fluidly communicates with the working fluid reservoir and is configured to expand the working fluid; an absorbent storage reservoir containing an absorbent, wherein the absorbent reservoir fluidly communicates with the expander and is configured to receive and absorb the expanded working fluid; a first heat exchanger that thermally communicates with the absorbent reservoir and is configured to transfer heat generated by the absorption of the working fluid by the absorbent to the working fluid during the discharge of the system; a pressure release mechanism configured to reduce pressure in the absorbent reservoir; a compressor that fluidly communicates with the absorbent reservoir and fluidly communicates with the working fluid reservoir and is configured to compress the working fluid that desorbs from the absorbent; and a second heat exchanger in thermal communication with the working fluid in the compressor, in thermal communication with the absorbent and working fluid in the absorbent storage tank, and configured to transfer heat that is generated by the compression of the working fluid, to the absorbent and working fluid in the absorbent storage tank.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of an embodiment of the mechanical-chemical energy storage system of the present invention being charged.

FIG. 2 is a schematic diagram of an embodiment of the mechanical-chemical energy storage system of the present invention being discharged.

FIG. 3 is a schematic diagram of an embodiment of the mechanical-chemical energy storage system of the present invention being discharged.

FIG. 4 is a schematic diagram of an embodiment of the mechanical-chemical energy storage system of the present invention being charged.

FIG. 5A is a schematic of an embodiment of the mechanical-chemical energy storage system of the present invention being discharged.

FIG. 5B is a schematic of an embodiment of the mechanical-chemical energy storage system of the present invention being charged.

FIG. 6A is a schematic of an embodiment of a mechanical-chemical energy storage system being discharged.

FIG. 6B is a schematic of an embodiment of a mechanical-chemical energy storage system being charged

FIG. 7A is an illustration of a top view of a heat exchanger in accordance with the present invention having high surface area fin-shaped structures (“fins”) integrated with an absorbent storage tank.

FIG. 7B is an illustration of a side view of a heat exchanger in accordance with the present invention having high surface area fin-shaped structures (“fins”) integrated with an absorbent storage tank.

FIG. 8A is a side view of a mechanical-chemical energy storage system according to the present invention.

FIG. 8B is a top view of a mechanical-chemical energy storage system according to the present invention.

FIG. 9 is a graph of CO₂ working fluid pressure versus the concentration of CO₂ in an amine generated using a computer model of an embodiment of the present invention.

FIG. 10 is a graph of CO₂ working fluid partial pressure in a CO₂/amine solution versus the concentration of CO₂ in an amine generated using a computer model of an embodiment of the present invention.

FIG. 11 is a graph of uptake of several metal organic frameworks and activated carbons as a function of pressure, generated using a computer model of embodiments of the present invention.

FIG. 12 is a graph of flux versus pressure of working fluid CO₂ generated using a computer model of an embodiment of the present invention.

FIG. 13 is a schematic process flow diagram using separate working fluid and adsorption/desorption streams in accordance with the present invention.

FIGS. 14A-14C are schematics of the processes involved in the charge, discharge, and throttle cycles in accordance with the present invention.

FIGS. 15A and 15B are schematics of a mechanical-chemical energy storage system according to the present invention.

FIG. 16 is a schematic of the processes involved in the charge and discharge of a mechanical-chemical energy storage system according to the present invention.

FIG. 17A is a graph showing differential enthalpies of absorption of carbon dioxide in 2.5 wt % aqueous ammonia in a reactor at 40° C.

FIG. 17B is a graph showing differential enthalpies of absorption of carbon dioxide in 2.5 wt % aqueous ammonia in a reactor at 60° C.

FIG. 17C is a graph showing differential enthalpies of absorption of carbon dioxide in 2.5 wt % aqueous ammonia in a reactor at 80° C.

FIG. 18 is a graph of temperature of the absorbed CO₂/MEA mixture as a function of the weight percent of CO₂ absorbed in MEA, generated using a computer model of an embodiment of the present invention.

FIG. 19 is a graph of expander power as a function of inlet temperature at several outlet pressures, generated using a computer model of an embodiment of the present invention.

FIG. 20 is a graph of compressor power as a function of inlet temperature at several inlet pressures, generated using a computer model of an embodiment of the present invention.

FIG. 21 is a graph of net power as a function of inlet temperature to the compressor for one-, two-, and three-stage compressions, generated using a computer model of an embodiment of the present invention.

FIG. 22 is a graph of RTE as a function of inlet temperature to the expander for one-, two-, and three-stage compressions, generated using a computer model of an embodiment of the present invention.

FIG. 23 is a graph of RTE as a function of expander inlet temperature, generated using a computer model of an embodiment of the present invention.

These figures are provided by way of example and are not intended to limit the scope of the invention.

DETAILED DESCRIPTION

In one aspect, the invention relates to the storage and delivery of energy as mechanical energy. In as much as mechanical and electrical energy are easily interchanged at high efficiencies by motors and generators, the system may also function as a “battery” even though there are no electrochemical reactions involved in the storage of energy by this invention notwithstanding the incidental use of conventional batteries for some system functions.

In another aspect, the invention relates to a chemical and thermodynamic system for energy storage. Energy is stored and released using distinct charge and discharge processes. This system simultaneously compresses a working fluid to a higher enthalpy state and recovers the heat of compression by driving a reversible chemical reaction. The compressed fluid is then expanded to a lower enthalpy state and chemically absorbed, driving the reverse exothermic reaction, from which heat can be supplied to increase the expansion efficiency.

During the discharge process, compressed working fluid (e.g., liquefied or supercritical gas) from a storage tank is expanded through an expansion device such as a turbine, piston, or nozzle, thereby generating power. The expansion results in cooling of the working fluid. The expanded working fluid (gas) exiting the expansion device undergoes a reversible chemical reaction with an absorbent that releases heat (exothermic). The heat is captured, for example by a heat exchanger, and the heat is transferred to the compressed working fluid that has yet to undergo expansion. This transferred heat beneficially increases the enthalpy of the working fluid prior to expansion, thus allowing for greater energy production. The process can continue until the compressed working fluid storage tank is empty.

During the charge process, the absorbed working fluid is desorbed through an endothermic reaction that is driven by a reduction in the pressure of the working fluid and absorbent. Energy is provided to a compression device that compresses the working fluid to a liquid or supercritical state and is stored in a storage tank. Heat from the compression process is captured and transferred to drive the endothermic desorption reaction. The process can continue until all of the working fluid has been desorbed and stored in the storage tank.

The systems and methods of the present invention have some or all of the following properties:

-   -   High RTE.     -   A high energy density due to high density material forms.     -   A closed cycle device not limited to air or nitrogen as a         working fluid.     -   Scalable using existing equipment for power generation and         handling of liquefied gases.     -   Energy and power performance specifications can be designed         independently of each other.     -   Very low cost.     -   Extremely, long cycle life     -   No self-discharge as heat is never stored as sensible heat but         only as chemical potential.     -   Ability to use waste heat or extract heat from the atmosphere to         achieve even greater energy conversions.

I. Definitions

For brevity, from hereon we will refer to the “grid” as being any application or solution for which the invention is suitable. We shall also refer to the operation of any of these systems in which energy is put into the device to charge it, as “charging” or “recharging”. Consistent with this definition, when energy is taken out of the device it is referred to as “discharging”. Any cycle of charge (partial or full) and discharge (partial or full) will simply be referred to as a “cycle”.

As used herein, “chemical absorption” refers to absorption using a chemical bond of a covalent pair to form either a solution or compound.

As used herein, the term “tank” and “reservoir” are used interchangeably to refer to a storage chamber.

As used herein, “desorption” is a process that is the inverse of absorption whereby some, or all, of an absorbed substance is released. Specifically, desorption is the process by which the molecules of a covalent pair are separated from each other in order to form, or reconstitute the original, prior to absorption, covalent pair.

For brevity, embodiments of the invention may be described as involving either an “absorption” or “adsorption” process. It will be understood to the reader that either process may be used in the embodiments of the invention depending on the choice of materials. Similarly, the terms “absorption agent”, “absorbent”, or “sorbent” are used interchangeably and may each refer to either a liquid or a solid agent that can absorb or adsorb a fluid, respectively.

As used herein, “round trip efficiency” or “RTE” is calculated as the power produced during expansion divided by the power required for compression.

As used herein, “activated carbon” is a form of carbon processed to be riddled with small, low-volume pores that increase the surface area available for adsorption or chemical reactions.

As used herein, the term “metal organic framework” refers to crystalline compounds consisting of metal ions or clusters coordinated to organic molecules to form one-, two-, or three-dimensional structures. In some cases, the structures are porous and the pores are stable during elimination of the guest molecules (often solvents) and can be used for the storage of gases.

As used herein, the term “food oil” refers to oils commonly used in cooking and food preparation including olive oil, palm oil, soybean oil, canola oil (rapeseed oil), pumpkin seed oil, corn oil, sunflower oil, safflower oil, peanut oil, grape seed oil, sesame oil, argan oil, rice bran oil and other vegetable oils.

As used herein, the term “silicone oil” refers to any liquid polymerized siloxane with organic side chains. Examples of silicone include are hexamethyldisiloxane and simethicone.

As used herein, the terms “first” and/or “second” do not refer to order or denote relative positions in space or time, but these terms are used to distinguish between two different elements or components. For example, a first component does not necessarily proceed a second component in time or space; however, the first component is not the second component and vice versa. Although it is possible for a first component to precede a second component in space or time, it is equally possible that a second component precedes a first component in space or time.

II. SYSTEMS

Referring to FIGS. 1-4, one embodiment of the present invention provides a system for storing energy comprising an absorbent tank or reservoir D, wherein the absorbent tank stores an absorbent capable of dissolving a working fluid; a compressor B that compresses a working fluid; a heat exchanger A (e.g., an ambient air vaporization heat exchanger) that transfers heat to or from the compressed working fluid; a working fluid tank or reservoir G that receives and stores the compressed cooled working fluid; and an expander H through which the compressed working fluid undergoes volumetric expansion. Some examples optionally comprise additional heat exchangers C, E, F, I, and J that can cool or heat a working fluid or mixture of a working fluid and absorbent.

In this embodiment, the system undergoes charging or recharging when desorbed working fluid (e.g., working fluid in a liquid physical state) is channeled from the absorbent tank or reservoir to the compressor (e.g., a piston cylinder) along flow pathway 1 where the working fluid is compressed. From the compressor, the compressed working fluid is channeled along flow pathway 2 to a heat exchanger that cools and/or condenses the compressed working fluid. The cooled and/or condensed working fluid is channeled along flow pathway 3 to the working fluid tank where it is stored until the system discharges energy. During the charging process, heat may be transferred in a closed loop, along flow pathways 4 and 5, from the compressor to the absorbent tank to enhance the efficiency of the system.

In this embodiment, the system undergoes discharging when desorbed working fluid is channeled from the working fluid tank, along flow pathways 6 and 7, to one or more heat exchangers that transfer heat to the working fluid. From the one or more heat exchangers, the heated working fluid is channeled, along flow pathway 8, to the expander wherein the working fluid undergoes volumetric expansion. Energy is discharged from system from the expander that may be coupled with a generator for producing electrical energy. The expanded working fluid, i.e., working fluid in a gaseous physical state, is channeled, along flow pathways 9 and 10, to the absorbent tank, wherein the working fluid is mixed or dissolved in the absorbent. In some embodiments, heat flows, along flow pathway 11, from one or more heat exchangers to the condensed working fluid before the fluid is expanded. After the working fluid is expanded, the one or more heat exchangers can transfer heat, along flow pathway 12, away from absorbent tank where heat is generated during the dissolution of the working fluid in the absorbent.

Alternatively, the system of the present invention may undergo discharging when desorbed working fluid having a liquid physical state is channeled, along flow pathway 13, to an expander wherein the liquid working fluid is transformed into an expanded vapor. The expanded vapor is channeled, along flow pathways 14 and 15, to one or more heat exchangers that transfer heat to or from the expanded vapor. The working fluid is then channeled, along flow pathway 16, to the working fluid tank, where it is stored until the system undergoes charging or recharging.

The system may undergo charging when desorbed working fluid is channeled, along flow pathways 17 and 18, from the working fluid tank to one or more heat exchangers and, along flow pathway 19, to the compressor, wherein the working fluid is compressed. From the compressor, compressed working fluid is channeled to one or more heat exchangers, along flow pathways 20-22, to the absorbent tank wherein the working fluid is mixed or dissolved in the absorbent.

Another aspect of the present invention relates to an energy storage system comprising: a working fluid reservoir containing compressed working fluid; an expander that fluidly communicates with the working fluid reservoir and is configured to expand the working fluid; an absorbent storage reservoir containing an absorbent, wherein the absorbent reservoir fluidly communicates with the expander and is configured to receive and absorb the expanded working fluid; a first heat exchanger that thermally communicates with the absorbent reservoir and is configured to transfer heat generated by the absorption of the working fluid by the absorbent to the working fluid during the discharge of the system; a pressure release mechanism configured to reduce pressure in the absorbent reservoir; a compressor that fluidly communicates with the absorbent reservoir and fluidly communicates with the working fluid reservoir and is configured to compress the working fluid that desorbs from the absorbent; and a second heat exchanger in thermal communication with the working fluid in the compressor, in thermal communication with the absorbent and working fluid in the absorbent storage tank, and configured to transfer heat that is generated by the compression of the working fluid, to the absorbent and working fluid in the absorbent storage tank.

In some embodiments, the working fluid comprises carbon dioxide, freon, methane, ammonia, nitrous oxide, air, or water.

In some embodiments, the working fluid comprises carbon dioxide.

In some embodiments, the absorbent comprises an organic amine, inorganic base, activated carbon, silica gel, zeolite, or metal organic framework.

In some embodiments, the absorbent comprises an organic amine selected from monoethanolamine, piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, or diethylenetriamine. For example, the absorbent comprises monoethanolamine (MEA). In some embodiments the absorbent comprises a mixture of MEA and water.

In some embodiments, the working fluid comprises ammonia.

In some embodiments, the absorbent comprises a metal halide salt (e.g. MgCl₂ or CaCl₂), mild acid, water, activated carbon, silica gel, zeolite, or metal organic framework.

In some embodiments, the working fluid comprises nitrous oxide.

In some embodiments, the absorbent comprises a food oil, silicone oil, activated carbon, silica gel, zeolite, or metal organic framework.

In some embodiments, the compressor and expander comprise a reversible turbine.

In some embodiments, the compressor comprises a turbine, piston, radial reaction turbine.

In some embodiments, the expander comprises a turbine, piston, or turbo-expander.

In some embodiments, the system further comprises an electrical generator connected to the expander.

In some embodiments, the system further comprises a motor connected to the compressor.

In some embodiments, the system further comprises an external heat source, in thermal communication with the expanded working fluid.

In some embodiments, the system further comprises a controller connected to the compressor (motor), expander (generator), pressure release mechanism, absorbent storage tank, working fluid storage tank, or any combination thereof.

In some embodiments, the first heat exchanger and second heat exchanger each comprise high surface area fin-shaped structures within the absorbent storage tank.

In some embodiments, the system further comprises one or more additional compressors, fluidly connected to and positioned between the first compressor and the working fluid storage tank.

In some embodiments, the system further comprises one or more additional expanders, fluidly connected to and positioned between the first expander and the absorbent storage tank.

In some embodiments, the pressure release mechanism is a valve.

In some embodiments, the system further comprises a pump that fluidly communicates with the absorbent storage tank and a sprayer in fluid communication with the pump and the absorbent storage tank. For example, the pump pumps the absorbent and absorbed working fluid to the sprayer and the sprayer sprays the fluid back into the absorbent storage tank. In some embodiments, the sprayer atomizes the fluid to small droplets. In some embodiments the sprayer sprays the absorbent over the heat exchanger with high surface area fin-shaped structures within the absorbent storage tank.

In some embodiments, the system further comprises a separator that fluidly communicates with the absorbent storage tank and the compressor. In some embodiments the separator is a centrifugal or cyclonic separator. In other embodiments the separator is a demister or a filter.

Another embodiment of the present invention, illustrated in FIGS. 5A and 5B, uses a liquid-density working fluid to store energy. FIG. 5A illustrates a system according to one embodiment of the present invention being discharged 200. The working fluid is stored in either a liquid or pressurized fluid state within the working fluid storage tank 202 until it is needed. Power is generated by allowing the working fluid to release from the working fluid storage tank 202 along flow path 210 and run through a heat exchanger 208, and then through flow path 212 into an expander 206 (e.g., a turbo-expander or piston expander) to produce work. After undergoing expansion, the working fluid is a low density vapor. This material is then channeled along flow path 214 to the absorber storage tank 204 and condensed using either a liquid or solid absorbent (or “sorbent”). In some embodiments, the absorbent-working fluid combination has a high heat of solution. The heat generated from mixing the two materials is transferred via heat exchanger 208 to heat the working fluid being delivered to the expander. At the end of a complete discharge, the working fluid storage tank will contain pressurized vapor, and the absorber tank will contain the absorbent saturated with working fluid.

FIG. 5B illustrates this system being charged or recharged 300. Recharging the system involves separating the working fluid from the sorbent and then channeling the working fluid along flow path 310 to the compressor 306 that compresses the working fluid and returns the working fluid to the working fluid storage tank 302 along flow paths 312 and 314. In several instances, the working fluid is separated from the absorbent either by decreasing the system pressure or increasing the system temperature, although other suitable methods of separation exist. During desorption, the working fluid undergoes cooling. The cooled working fluid may be used to condense the compressed vapor before returning the working fluid to its storage tank 302. In some embodiments, additional heat exchangers may be used to enhance heat removal, i.e., cooling. Tanks 302, 304 and heat exchanger 308 may be used in both discharge and recharge mode; and, only the compressor 306 and turbo-expander 206 are unique to each step. In some embodiments, a reversible turbine may be used that can be configured to function as either a compressor or expander as needed.

FIGS. 6A and 6B illustrate another embodiment of the present invention. The embodiment depicted in FIGS. 6A and 6B show the system of the present invention operating as an electrical energy storage system.

In FIG. 6A, the electrical energy storage system 10 is discharging energy (e.g., electrical energy). This system has a power side 12 and an energy side 14. The energy storage and power generation may be designed to give a wide range of combinations of energy and power for many applications. The working fluid or gas exits working fluid tank 34 along flow path 46. As the working fluid or gas exits the working fluid tank, it passes through one or more heat exchangers 30, 32. The heat exchangers capture the heat of reaction between the working fluid (e.g., CO₂) and the absorbent (e.g., an amine absorbent). The reaction occurs on the outer surface of the heat exchanger 30 and the heat from this reaction is transferred to the working fluid (e.g., CO₂) in the pipe of the heat exchanger. The heated working fluid (e.g., CO₂) is transported along flow path 40 to the expander 22 where the compressed or pressurized working fluid (e.g., CO₂) expands to generate energy. In some embodiments, the expander is connected to a gearbox 18 and a generator 16 through any suitable mechanical connection to generate the desired electrical output. The expander (e.g., turbine) may be connected to a generator of any type (e.g., AC, DC, 3-phase, or the like) or the shaft power may be used for any desired purpose. Optionally, an additional heat exchanger 26 may provide additional heat (e.g., sourced from waste heat or other heat source) to the working fluid prior to expansion. After expansion, the working fluid may flow through an optional separator 24, and then into the absorber tank 28.

There are several suitable expansion type devices available to recover the energy from expanding gases. These can be of any design and include both turbines and piston type motors. In general, the turbines, when used in this application, are commonly called “turbo-expanders”. In some embodiments, the expander or turbo-expander obtains conversion efficiency in excess of about 80% of the energy in the expanding gas. In other embodiments, the turbo-expander obtains about 90% efficiency. In some embodiments, the expander is a radial reaction turbine (RRT). And, in some embodiments, the RRT is configured to run with supercritical working fluids, such as CO₂, to achieve high efficiencies. To use an RRT, the absorbent(s) are selected that match the pressure range of the output of the RRT in the system.

The critical temperature of CO₂ is 31° C. At this temperature, the pressure of the CO₂ is 56 bar. In some instances, the pressures in the RRT vary between about 50 bar and about 120 bar. If a solid absorbent is paired with a supercritical working fluid (e.g., CO₂), the heat transfer associated with the solid absorbent will be improved because supercritical fluids are efficient heat transfer agents.

As illustrated in FIG. 6A, during the discharge, the rate of discharge is regulated by the rate of the working fluid passing through the turbo-expander. Increases in flow rate are associated with increases in power output. Power output may be controlled by standard control valves or mass flow controllers. A higher flow rate also means that more working fluid (e.g., CO₂) is entering the absorbent reservoir and more heat is generated from the reaction of the working fluid with the absorbent. This heat corresponds with the increased amount of working fluid that requires heating at these higher rates. Thus, heat is generated in suitable amounts as needed, and there is no requirement to store a hot gas or liquid for use at a later time.

In systems of the present invention, heat exchangers can possess any suitable configuration. FIGS. 7A and 7B illustrate one configuration for optional heat exchanger 26 in accordance with the present invention. In this configuration, cold working fluid or a mixture of cold working fluid and cold absorbent is channeled through serpentine piping 550 that thermally communicates with heat exchanger fins 510. Cold working fluid or mixture enters the serpentine piping 530 and exits as heated working fluid or a heated mixture 540. This optional heat exchanger can also be used to extract heat from other sources such as waste heat in any form or even from the environment if the ambient temperature is above the temperature of the fluid or gas entering the turbo-expander.

Referring to FIG. 6A, the absorbent is a pumpable liquid that may be pumped along flow path 38 by pump 20, in this example, directly over the heat exchanger 30 and stored in the working fluid storage tank. In some embodiments, an exothermic chemical reaction occurs between this liquid and the incoming working fluid (e.g., CO₂), and heat is generated directly on fins of the heat exchanger 30 within the absorbent reservoir.

The working fluid travels along flow paths 44, 130, and 138 to a compressor. Electrical energy runs motor 106 that compresses or increases the pressure of the working fluid. The motor may operate compressor 108 or the motor may reverse the operation of turbo-expander so that the turbo-expander functions to compress the working fluid. Any suitable compressor can be used to complete this step. The pressurized work fluid is channeled along flow path 128, 134, and 136 to the working fluid storage tank, where it is stored until a discharge cycle begins.

As illustrated in FIGS. 8A and 8B, the compressor and expander (e.g., turbo-expander) may be different devices, or the turbo-expander may also act as the compressor. In this embodiment, absorbent pump 890 pumps absorbent to distribution manifold 870 wherein the absorbent is sprayed from spray nozzles 881-884 onto the heat exchanger 900 that comprises spirally wound pipe that channels working fluid to the expander and/or from the compressor. As illustrated, systems of the present invention may optionally include one or more pall rings 851-854 inside the absorbent tank and/or inside the working fluid tank. Moreover, the charging and discharging of systems of the present invention may also be accomplished using a controller such as valve 860, which operates to control the flow path for the working fluid during charging and discharging.

Depending on how much pressure change is desired in the cycle, the compressor may be one or more (e.g., 1, 2, 3, 4, or more) stages. The choice of pressure range is governed by design choices based on absorbent properties and the desired energy density. Energy density is related to the operating pressure since, as can be seen by FIGS. 9-11 that typical absorbents give different amounts of working fluid (e.g., CO₂) capacity depending on pressure and temperature. Thus, if an absorbent that can absorb (and release during recharge) more working fluid (e.g., CO₂) than another absorbent will have a better energy density compared with the other absorbent that does not absorb as much working fluid (e.g., CO₂) per unit volume of absorbent.

As shown in FIG. 12, heat flux is given in units of area and time. Thus, greater surface area of heat exchanger fins leads to higher reaction rates and allows for faster working fluid (e.g., CO₂) absorption and higher power generation. Moreover, this heat does not need to be transported or stored. It is available to go directly back to the working fluid that is about to be expanded in the expander (e.g., turbo-expander or piston). Alternatively, excess heat could be transferred to a secondary heat transfer fluid that could then be pumped to a site where heat is desired.

In some embodiments, the vacuum action of the intake side of the compressor will be sufficient to allow working fluid (e.g., CO₂) to be released from the absorbent. In these embodiments, this is an endothermic reaction and the absorbent will cool. However, the action of compressing the working fluid will generate heat. In some embodiments, this heat is removed to maintain efficiencies. Further, the absorbent cannot cool indefinitely, so as the absorbent cools, heat generated in the compressor heats the absorbent. The heat going to the absorbent may drive the endothermic reaction and facilitate the release of additional working fluid (e.g., CO₂) for compression. This continues until the working fluid (e.g., CO₂) tank is full or until it is desired to stop the recharging process.

Accordingly, systems of the present invention may be charged or discharged and reversed at any part of the cycle. These systems may also be run at any power level even its maximum power right to the very end of the cycle. It may be discharged to 100% depth of discharge as often as desired and at full power as well with no detrimental effects to the system.

In some embodiments, during the recharge cycle, as the working fluid (e.g., CO₂) is being released from the absorbent, some absorbent may become entrained in the working fluid. Should this be the case, an optional separator 24 may be placed between the absorbent reservoir and the intake to the expander (e.g., turbo-expander). In some embodiments, such as the embodiment illustrated in FIGS. 6A and 6B, the separator is a centrifugal or cyclonic separator. In other embodiments, the separator may comprise a simple demister or filter.

Another embodiment of the mechanical-chemical energy storage system is described in the schematic diagram shown in FIG. 13. This closed loop system contains several loops. In this embodiment, to avoid any corrosion of compressor blades, precautions are taken to prevent the entry of absorbent (e.g., ammonia) or working fluid-absorbent mixture (e.g., carbon dioxide ammonia mixture) into compressors. Starting with the fully charged system, high pressure carbon dioxide (labeled “high pressure CO₂”) expands through an expansion device or series of expansion devices E1-E3 to generate power. Examples of suitable expansion devices include turbo-expanders.

In one loop, the expanded working fluid (e.g., CO₂) or exhaust from the expansion device travels through heat exchanger (Hx3). Later, this low-pressure working fluid (e.g., CO₂ gas) labeled “low pressure CO₂” is compressed by one or more compressors C1-C5 returning to higher pressure carbon dioxide phase. During the compression of the carbon dioxide gas, which is an exothermic process, heat is captured by one or more heat exchangers H_(x) 4-H_(x) 7.

In another loop, the expanded working fluid or exhaust from the expansion device reacts with an absorber (e.g., aqueous ammonia (˜36% solution)) in an exothermic reaction that generates heat while absorbing the working fluid (e.g., CO₂). Thus, this additional energy increases the enthalpy of the working fluid allowing for a greater energy production from this part of the cycle. Since the temperature of the absorbent is higher than the temperature of the cooling working fluid, energy will naturally flow in the desired direction shown by the arrow in the discharge portion of FIG. 13. Higher pressures and lower temperature of operation benefit reductions of absorbent (e.g., ammonia) concentration in the working fluid (e.g., CO₂) phase. This heat energy powers the transfer of the organic amine (e.g., aqueous ammonia) and working fluid (e.g., CO₂) solution to a reboiler kept to a temperature of about 180° F., wherein the solution separates into the working fluid (e.g., CO₂ gas) and the organic amine (e.g., aqueous ammonia). The partial amount of wet working fluid (e.g., CO₂) and absorbent (e.g., ammonia gas) is pumped into the heat exchanger chamber containing Hx1-Hx2. During this process further separation of working fluid (e.g., CO₂) and absorbent (e.g., ammonia) occurs and the gas passing through the heat exchanger Hx3 is essentially pure working fluid (e.g., CO₂). Later, this low-pressure working fluid (e.g., CO₂ gas) labeled “low pressure CO₂” is compressed by one or more compressors C1-C5 returning to higher pressure carbon dioxide. Thus, the working fluid (e.g., CO₂ gas) enters into the next cycle.

In another loop, the low concentration liquid working fluid and absorbent solution (e.g., CO₂ and ammonia solution) exiting the reboiler is circulated into the chamber containing Hx1 and Hx2 heat exchangers. Working fluid gas (e.g., CO₂ gas) is further separated from absorbent (e.g., ammonia) in this chamber and circulated via heat exchanger Hx3 into compressors C1-C5. Thus, the working fluid (e.g., CO₂) gas enters into the next cycle.

Another embodiment of the mechanical-chemical energy storage system is described in the schematic diagrams shown in FIGS. 15A and 15B. During discharging, high pressure working fluid undergoes expansion wherein the expander (e.g., a turbine or turbo-expander) can generate electrical energy when coupled with a generator. The expanded working fluid is absorbed by the absorbent in a reaction vessel. When the system is charged, the working fluid is separated from the absorbent and channeled to a multistage compressor wherein the working fluid is pressurized and returned to a working fluid tank as a high pressure working fluid. The heat generated during the compression of the working fluid may be transferred to the reaction vessel to power the release of the working fluid via a heat exchanger, or the heat may be transferred to high pressure working fluid before it is expanded through the expander.

Working Fluids

All suitable working fluids are within the scope of the invention. Suitable working fluids can be expanded and compressed and can be absorbed by an absorbent. Exemplary working fluids include fluids that can be compressed to a liquid, critical, or trans-critical state at the desired operating pressures and temperatures. For example, the desired temperature may be ambient temperature (about 20 to 25° C.) and the desired pressure range may be from about 40 to 60 bar, thus, exemplary working fluids would be in a liquid, critical, or trans-critical state at those conditions. Some exemplary working fluids will be absorbed by the absorbent in a reversible and/or exothermic process. Some specific exemplary working fluids include carbon dioxide (CO₂), ammonia (NH₃), nitrous oxide (N₂O), air, and water.

Examples of suitable working fluids are described in Table 1.

TABLE 1 Working fluids. Latent Melting Heat of Point Working Fluid Additive Fusion (J/g) (° C.) Fatty Acids Hexadecane Na Mont- 126 — morillonite Fatty acids Surfactants 191 — Oleic acid CuO — — Myristic acid palmitic acid 190 61 Capric acid — 170 36 Capric acid Nanotubes  75 36 Lauric acid — 188 49 Myristic acid — 201 61 Palmitic acid — 185-220 67 Stearic acid — 220 73 Dodecanoic acid — 190 42 Lauric acid/stearic — 131 33 acid Stearic acid Bentonite  84 73 Paraffins Paraffin — 173 64 Paraffin waxes Nanotubes — 60 Paraffin Graphite 180 40 Paraffin SiO₂ 110 — Paraffin Fe₂O₃ — 47 Paraffin Siloxane 160 35 Nonacosane — 240 64 Hexacosane — 257 56 Organics Tetrabutylammonium — 200 — clathrates Tetradecanol Graphite 220 36 Naphthalene — 148 80 Erytritol — 340 118  Camphene — 238 50 1,3-ditetradecanoyl — 126 48 thiourea Salt Hydrates Glauber's salt polyacrylomide 270 32 (Na₂SO₄ *10H₂O) Glauber's salt Gelatin 248 — (Na₂SO₄ *10H₂O) Hydrate salts — 103 21 CaCl₂/MgCl₂ + SrCl₂ Na₂CO₃*10H₂O — 247 33-36 NaHPO₄*7H₂O — 135-170 48 MgSO₄*7H₂O — 202 49 Ba(OH)₂*8H₂O — 265-280 78 CH₃COONa*3H₂O — 270-290 58 CH₃COONa*3H₂O Graphite — — NaOH*H₂O — 272 58 Eutectic Mixtures Naphthalene + Benzoic — 123 67 acid AlCl₃ + NaCl + ZrCl₂ — 234 68 Long Chain Polymers PEO carbon black 120-170 60 PEO Graphite 130-160 60 PEO carbon fibers 140-180 60 PEO Fullerenes 160-180 60 PEO SWCNT 150-180 60 PEO Cellulose  40-130 60 PEO Starch 47-97 60 PEG Chitosan 140 ~50   PEG Cellulose  60 ~50   PEG 35,000 — 167 68 PEG 35,000 lauric acid 186 43-56 PEG 3400 lauric acid 188 43-54 Dissolved Gases¹ SO₃ — 331 62 CO₂ — — — NH₃ — — — N₂O — — — halons — — — alcohol vapor — — — gaseous hydrocarbons — — — freons — — — Molten Salts Na₂SO4*10H₂O — —   32.4 Solid PCM Pentaglycerin — 192 81 2-amino-2-methyl- — 264 78 1,3-propanediol Misc. Materials oleochemical — 144-227 from −6 to 47 carbonates ¹Possible solvents for freons, hydrocarbons and Nitrous oxide include butanediammine, 2-diethylamino ethanol, aqueous Na glycinate solution, diethanolamine, olive oil, aqueous hydroxide solution, dodecane, ammonia water, amine based solvent (e.g., Stonvent), vegetable oil, paraffins, or any combination thereof.

Absorbents

All suitable absorbents are within the scope of the invention. Suitable absorbents agents are capable of chemically absorbing a working fluid. Exemplary absorbents will absorb the working fluid in a reversible and/or endothermic process. Some specific exemplary absorbents include: absorbents of carbon dioxide, such as organic amines (e.g., monoethanolamine (MEA), piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, or diethylenetriamine), inorganic bases (e.g., potassium carbonate, ammonium carbonate), activated carbon, silica gel, zeolites, and metal organic frameworks; absorbents of ammonia, such as salts that form ammonates, halide salts (e.g., magnesium chloride (MgCl₂), calcium chloride (CaCl₂)), mild acids, water, activated carbon, silica gel, zeolites, and metal organic frameworks; absorbents of nitrous oxide, such as oils that dissolve nitrous oxide (e.g., food oils, silicone oils), activated carbon, silica gel, zeolites, and metal organic frameworks; and absorbents of air such as activated carbon and zeolites. The terms “absorption agent”, “absorbent”, and “sorbent” are used interchangeably and may each refer to either a liquid or a solid agent that can absorb or adsorb a fluid, respectively.

Examples of pairs of absorbents and working fluids suitable for use in the present invention are described in Table 2

TABLE 2 Working fluids and absorbents. Working H_(ads), Fluid Absorbent (kJ/mole) Pressure CO₂ CO₂ silicas  ~5-15 — CO₂ organic and inorganic  ~1-40 — carbonates CO₂ absorbent carbons  ~5-15 — CO₂ clays ~5-5 — CO₂ aluminas  ~5-15 — CO₂ zeolites  ~5-15 — CO₂ amine and methyl <5 ~1 bar substituted MOF CO₂ various coals ~12-13 up to 200 bar CO₂ MOF ~16-20 — CO₂ carborane based MOF ~22 up to 10 bars CO₂ DABCO based MOF ~20-24 up to 25 bars CO₂ MOF ~22-24 — CO₂ Au in range of — 22-26 CO₂ zeolitic imidazolate ~21-30 — CO₂ modified MOF ~26 — CO₂ MOF BTC framework   27-37 — CO₂ carbon sorbent     28-25.7 ~1 bar CO₂ Cr-phthalate ~30 up to 30 bar CO₂ Zeolite 13X ~31 ~2 bar CO₂ MOF ~33, ~22 up to ~5 bar CO₂ chabazite ~35 — CO₂ fluoro-functionalized ~45 — metal oxide framework decreasing to ~30 CO₂ metal oxide framework ranges from 1-50 bar 16-41 CO₂ silica foam 43 up to 1 bar CO₂ unsaturated metal 22, 32, 45, — centers 47-52, 44-54 CO₂ zeolite 13X and 46 and 41 1 bar Mg₂(dobdc) respectively CO₂ molecular porous ~47 — material CO₂ benzene-dicarboxylate   30-50 — CO₂ methyl diethanolamine ~50-58 — (aq) CO₂ ionic liquids 80 2-3 bar CO₂ chabazite zeolites — up to ~10 bar CO₂ hydromagnesite — — CO₂ imidazolium based ionic — up to ~20 bar liquids CO₂ MOF — 0-5 bar CO₂ Zn(II) -cyclen — — CO₂ silicon nitride — — CO₂ TBAB (aq) — — CO₂ Triethylbutylammonium — — Acetate CO₂ porous organic — — polymers CO₂ clathrate hydrates — — CO₂ aminosilicates — — CO₂ Hydrated salts — — CO₂ MOF 177 — up to 20 bar CO₂ Triethylbutyl — — ammonium acetate CH₄ CH₄ various carbons ~10-11 — CH₄ various coals ~10-11 — CH₄ MOF ~11-12 — CH₄ zeolites ~14 90 bar decreasing to ~6 CH₄ carborane based MOF ~15 20 bar CH₄ zeolite 13X 15 ~2 bar CH₄ DABCO based MOF ~14 to ~18 25 bar CH₄ zeolite templated carbon   16-20 — CH₄ MOF ~21, ~18 up to ~5 bar NH₃ NH₃ salt ammonates    5-45 — (CaCl₂*6NH₃) NH₃ thiocyanate — — NH₃ ammonia borane — 1-4 bars NH₃ CaCl₂ - vermiculite ~40 up to 4 bar NH₃ SrCl₂ - amine ~33 ~2 bar NH₃ MgCl₂   55-87 5 bar NO₂ NO₂ biochar 20-27 for ~1 bar biochar, ~10 for Al₂O₃, Fe₂O₃ and peat CO CO DABCO based MOF ~10 to ~12 25 bar CO MOF ~45, ~23 up to ~5 bar CO Ni or Fe powder — — CO CO complexes — — Ar, N₂, O₂ Ar, N₂, O₂ carbon sorbent   16-17 ~1 bar H₂ H₂ zeolite 3.5 and — higher Ne Ne chabazite ~5 — Ar Ar chabazite ~15 — Ar various coals ~14-16 — ethylene + ethylene + NaX zeolite   28-40 — ethane ethane N₂ N₂ various coals ~8 — freons, freons, various carbons ~8 — halons halons freons, various silicas ~8 — halons freons, various zeolites ~8 — halons freons, various clays ~8 — halons freons, various MOF's ~8 — halons freons, various aluminas ~8 — halons freons, graphene ~8 — halons freons, graphite oxide ~8 — halons freons, various MOF's ~8 — halons freons, various MOF's ~8 — halons NO NO NO complexes ~10-20 — H₂O H₂O salt hydrates 5 to 45 — H₂O silcas 5 to 45 — H₂O zeolites 5 to 45 — H₂O aluminas 5 to 45 — H₂O various MOF'scarbons 5 to 45 — H₂O inorganic and organic 5 to 45 — oxide-hydroxides both

III. Mechanical Chemical Energy Storage Methods

One aspect of the invention relates to a method for storing energy comprising: providing an absorbent reservoir containing a working fluid that is chemically absorbed by an absorbent; desorbing the working fluid from the absorbent in an endothermic process; and condensing the working fluid in an exothermic process and transferring the condensed working fluid to a working fluid reservoir under pressure wherein at least some of the heat generated during the condensing step is recycled to drive the desorbing step.

In some implementations, the working fluid comprises carbon dioxide, ammonia, nitrous oxide, air, or water.

In some implementations, the working fluid comprises carbon dioxide or ammonia.

In some implementations, the absorbent comprises an organic amine, an inorganic base, an activated carbon, silica gel, a zeolite, a metal organic framework, or any combination thereof.

In some implementations, the absorbent comprises an organic amine selected from monoethanolamine, piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, diethylenetriamine, or any combination thereof. For example, the absorbent comprises monoethanolamine (MEA).

In some implementations the absorbent comprises a mixture of MEA and water.

In some implementations, the working fluid comprises ammonia.

In some implementations, the absorbent comprises a metal halide salt, a mild acid, water, activated carbon, silica gel, a zeolite, or metal organic framework.

In some implementations, the working fluid comprises nitrous oxide.

In some implementations, the absorbent comprises a food oil, silicone oil, activated carbon, silica gel, zeolite, or metal organic framework.

In some implementations, the heat generated from the condensing step is recycled to drive the desorbing step using a heat exchanger.

In some implementations, the method further comprises compressing the working fluid using a reversible turbine.

In some implementations, the method further comprises compressing the working fluid and storing the working fluid in the working fluid reservoir in a liquid state, a critical state, or a trans-critical state.

In some implementations, the working fluid is compressed to and stored at a pressure of from about 1 bar to about 200 bar (e.g. 10 bar to 100 bar, or about 50 bar).

In some implementations, the method further comprises a second compression stage after the first compression.

In some implementations, the working fluid is expanded to a pressure of from about 0.1 bar to 10 bar (e.g., about 0.5 bar to about 5 bar, or about 1 bar).

In some implementations, the working fluid is stored at ambient temperature.

In some implementations, the method further comprises heating the working fluid prior to expansion using an outside heat source.

Another aspect of the invention relates to a method of charging and discharging an energy storage system comprising: (1) charging the system comprising: providing an absorbent storage tank containing a working fluid that is chemically absorbed by an absorbent; desorbing the working fluid from the absorbent in an endothermic process; condensing the working fluid in an exothermic process and transferring the condensed working fluid to a working fluid reservoir under pressure; and recycling heat generated during the condensing step to drive the desorbing step; and storing the working fluid in a working fluid reservoir under pressure; and (2) discharging the system comprising: expanding the working fluid; chemically absorbing the working fluid with the absorbent in the absorbent reservoir in an exothermic process; recycling heat generated during the absorption reaction to drive the expanding step; and storing the absorbent and the absorbed working fluid in the absorbent reservoir.

In some implementations, the working fluid comprises carbon dioxide, ammonia, nitrous oxide, air, or water.

In some implementations, the working fluid comprises carbon dioxide.

In some implementations, the absorbent comprises an organic amine, inorganic base, activated carbon, silica gel, zeolite, or metal organic framework.

In some implementations, the absorbent comprises an organic amine selected from monoethanolamine, piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, or diethylenetriamine. For example, the absorbent comprises monoethanolamine (MEA). In some implementations the absorbent comprises a mixture of MEA and water.

In some implementations, the working fluid comprises ammonia.

In some implementations, the absorbent comprises a metal halide salt (e.g., MgCl₂, CaCl₂), mild acid, water, activated carbon, silica gel, zeolite, or metal organic framework.

In some implementations, the working fluid comprises nitrous oxide.

In some implementations, the absorbent comprises a food oil, silicone oil, activated carbon, silica gel, zeolite, or metal organic framework.

In some implementations, the heat generated during the condensing step is recycled drive the desorbing step using a heat exchanger.

In some implementations, the working fluid is compressed by a reversible turbine.

In some implementations, the method further comprises compressing the working fluid and storing the working fluid in the working fluid reservoir in a liquid state, a critical state, or a trans-critical state.

In some implementations, the working fluid is compressed to and stored at a pressure of from about 1 bar to about 100 bar, (e.g. from about 10 bar to about 100 bar, from about 20 bar to about 80 bar, or about 50 bar).

In some implementations, the compressing step comprises a two-stage compression process.

In some implementations, the working fluid is expanded to a pressure of from about 0.1 bar to 10 bar (e.g. about 1 bar).

In some implementations, the working fluid is stored at ambient temperature.

In some implementations, the method further comprises beating the working fluid prior to expansion using an external heat source.

In some implementations, the method further comprises directing the flow of the working fluid a first direction during charging, and reversing the flow of the direction of the working fluid during discharging.

Another aspect of the mechanical-chemical energy storage systems of the present invention are illustrated in FIGS. 14A-14C. Starting with a fully charged system, as shown in FIG. 14C, the system uses CO₂ as a working fluid, but it is not limited to this working fluid. There is a full tank of a liquefied or supercritical CO₂ labeled “liquefied gas” that is expanded through an expansion device such as a turbo-expander to generate power. As the working fluid expands, its enthalpy reduces and it cools. The exhaust form the expansion device is now reacted with an absorber, such as an organic amine, such as MEA, that generates heat while absorbing the CO₂. This heat is beneficially used by transfer to the cooling CO₂ gas on the input side of the turbo-expander. Thus, this additional energy increases the enthalpy of the working fluid allowing for a greater energy production from this part of the cycle. Since the temperature of the absorbent medium is higher than the temperature of the cooling working fluid, energy will naturally flow in the desired direction shown by the arrow in the discharge portion of FIG. 14C. This process may continue at any desired rate or rates until all of the CO₂ or other working fluid has been removed from the tank. It is however, not necessary to completely discharge the tank, if it is desired to start a recharge cycle. It may be reversed at any time that is desired.

When it is desired to recharge the system, the reverse process is shown in the charge portion of FIG. 14B. Here, energy is input to reverse the chemical reaction and release the working fluid as a gas, which lowers the enthalpy of the absorbent. The working fluid gas is then compressed to the pressure required to create a liquid or supercritical fluid. During this compression, heat is generated. Recovering this heat via the use of a heat exchanger raises the RTE of the system. This heat is transferred to the absorbent(s). This heat continues to drive the release of the working fluid from the absorbent. This process may be continued at any desired rate or rates until the working fluid (e.g., CO₂) tank is full. In this embodiment, it is not necessary to completely recharge the tank. If it is desired to start a discharge cycle before the filling of the working fluid tank, the cycle may be reversed before the working fluid tank is full.

Another aspect of the present invention provides a method of storing energy using mechanical-chemical energy storage system is described in FIG. 16. This implementation comprises charging the system by compressing a working fluid (e.g., CO₂) in a series of compressors C10-C40, i.e., multi-stage compression, and storing the compressed working fluid in a working fluid tank. Charging, according to this implementation, also comprises removing or transferring the heat generated during the multi-stage compression from the working fluid using heat exchangers Hx40-Hx70 that are arranged between compressors or operated between successive compression stages.

Some implementations further include discharging energy from the mechanical-chemical energy storage system. Discharging energy from this system comprises expanding the working fluid through expanders (e.g., turbines, turbo-expanders, pistons, or any combination thereof) E10-E30. One or more heat exchangers Hx80, Hx10, and Hx20 transfer heat to the working fluid. The one or more heat exchangers are arranged to input heat to the working fluid between successive expansions. In some instances, the heat exchangers are arranged along the working fluid flow path between expanders. Alternatively, a single heat exchanger can input heat to the working fluid between successive expansions.

IV. Examples Example 1: Ammonia and Magnesium Chloride

Magnesium chloride can form ammonates. MgCl₂ can absorb up to 6 molecules of ammonia to form MgCl₂*6NH₃.

The pressure of the ammonia over the MgCl₂ varies as more or less ammonia is incorporated into the molecular structure. Since the salt and its ammonate are solid, the heat generated from the reaction needs to be allowed to move to the cooling ammonia by either packing the salt on one side of a heat exchanger and having the ammonia on the other side of the same heat exchanger or by having an intermediate heat transfer fluid carry the heat away from the salt and deliver it to the ammonia.

Simplified chemical equations representing these reactions include:

MgCl₂+NH₃==>MgCl₂*NH₃  (1)

MgCl₂*NH₃+NH₃==>MgCl₂*2NH₃  (2)

MgCl₂*2NH₃+NH==>MgCl₂*3NH₃  (3)

MgCl₂*3NH₃+NH₃==>MgCl₂*4NH₃  (4)

MgCl₂*4NH₃+NH₃==>MgCl₂*5NH₃  (5)

MgCl₂*5NH₃+NH₃==>MgCl₂*6NH₃  (6)

As NH₃ pressure is increased all of the above reactions will go to completion (to the right). This is the case as the system is discharging.

These are also all exothermic reactions. Thus, the heat that is released can be used to expand the ammonia to get addition energy from the system. Note that this heat energy is generated when and as the system discharges. It is not stored as heat but used right away to create more energy and increase the efficiency of the system.

Further, removing ammonia during the recharge step will drive the reactions to the left and create a source of cold to help with the liquefaction of ammonia. Again this cold is not stored as a cold material but is generated as the recharging process takes place.

In this case, the vacuum at the intake of the compression device could be sufficient to start removing ammonia from the MgCl₂*NH₃ and drive the recharge reaction. The additional heat from the compression of the ammonia can also drive the release of the ammonia until the recharging is complete.

Example 2: Carbon Dioxide and Monoethanolamine

Monoethanolamine (MEA), usually as a 30% solution in water, has been used for many years for removal of CO₂ from natural gas.

The simplified chemical equations representing these reactions include:

CO₂+H₂O==>HCO₃ ⁻+H₊  (7)

MEA+HCO₃ ⁻==>MEAHCO₂ ⁻+H₂O  (8)

These reactions are exothermic and give off heat as CO₂ is absorbed. These are essentially simple acid-base reactions that are easily reversible since they are not too exothermic.

The fact that a gas is part of the equilibrium helps the reaction be driven in either direction by change of gas pressure. This allows for the storage of energy as chemical potential and allows for the control of this reaction by pressure and temperature.

Thus, as CO₂ exits the turbo-expander, the equilibrium in reaction 7 is pushed to the right, which also pushes reaction 8 to the right, releasing heat energy as needed to expand the CO₂ further.

FIGS. 7A and 78 shows one possible configuration of a heat exchanger for transferring heat. In the embodiment of FIGS. 7A and 7B, MEA (absorbent) is allowed to fall over the outer fins of a heat exchanger. While the CO₂ gas (working fluid) is allowed to react with the MEA in the same area. The high surface area fins increase the reaction rate by exposing a greater amount of MEA to the CO₂. As the MEA and CO₂ react, the heat is then directly available to any fluid inside the pipes of the heat exchanger. This can be the pressurized CO₂ going into the turbo-expander or it can be an intermediate heat exchange fluid (such as water) that can be pumped where the heat is desired.

FIG. 18 is a typical graph showing the rate of CO₂ absorption per unit area and time. FIG. 9 is a typical loading graph showing how much CO₂ can be absorbed at various pressures.

These relationships, shown in FIGS. 18 and 9, can be used to design systems with a CO₂ working fluid. The power and absorption rate can be calculated using FIG. 12 for the particular absorbent and pressure temperature ranges. The required amounts of CO₂ and (in this case MEA) can be calculated by determining how many moles of CO₂ are absorbed and released under the intended operating conditions of the system.

As an example, a system may have a vacuum side of the compressor that will operate at 100 pascals and will charge the MEA up to 100,000 pascals. The amount of CO₂ can then be calculated by finding those two points on the graph where the line crosses and reading down to how much CO₂ is absorbed by the MEA at those pressures. In this case, when charging at 100,000 pascals, the mole ratio is about 0.6 moles of CO₂ per mole of MEA. Down at the lower pressure the ratio is about 0.2 to 1. These two ratios are subtracted and it is determined that the capacity of the MEA operation between these pressures will cycle at about 0.4 moles of CO₂ per mole of amine. It should be noted that these curves are at a single temperature.

FIG. 10 shows that if the temperature is shifted in the correct direction that the capacity can also be increased. As the absorber is being charged if its temperature is lowered it will absorb more CO₂ at any given pressure. This is of course precisely what the invention does while the system is discharging. Further, as the absorbent is heated it will release more CO₂ than would otherwise be released at that same pressure. This is also precisely what happens during recharge when we would want more pressure at the intake side of the compressor.

FIG. 10 shows the pressure of CO₂ at 40 and 60° C. over MEA/PZ. As can be seen by the two lines in FIG. 10, at all points, the pressure of CO₂ at 60° C. is greater than that of CO₂ at 40° C. Thus, by coaling the MEA during absorption and heating during desorption and by using the chemical potential of the MEA reaction, the efficiency of the system is maximized. This graph also shows that an increase of about 0.2 moles of CO₂ per mole of amine can be obtained by swinging the temperatures between 40° C. and 60° C. during the discharge and recharging, respectively.

FIG. 11 shows an example of advanced metal organic frameworks (MOFs) and activated carbon. These materials have a high capacity for storage of carbon dioxide at room temperature. These materials have a wide range of pressures to choose from for design considerations and are in some cases capable of absorbing over 100% of their own weight in CO₂.

Example 3: Process Simulation No. 1—(CO₂/MEA)

In order to simulate an exemplary process, a CHEMCAD simulation software package was used. The process was simulated in sections rather than in a single simulation to allow for the use of different models for the fluid properties in certain segments of the process. Initial simulations were performed assuming a constant CO₂ mass flow rate (1 lb/sec) and assuming negligible carryover of any impurities or sorbents through the expansion/contraction steps. It is also assumed that the heat of solution of the CO₂ and sorbent is capable of heating the solution to the fixed set point temperature for the calculation. Therefore, it must be noted that the highest temperatures in the simulations below may not be achievable without additional heat input (this will be discussed further).

Using a single stage expander, FIG. 19 shows the variation of expander power output at varying process conditions. As would be expected, greater power output occurs at higher inlet temperatures and at larger pressure drops across the expander. For the expander, it is preferred to maximize the power output during the discharge step.

Referring to FIG. 20, a similar study was performed with the compressor. Similar results were obtained as to the expander; higher temperatures lead to higher power inputs to compress the CO₂, and a greater pressure difference across the compressor requires greater power input. Compression occurs during the recharge step, so it is preferred to minimize the power input to repressurize the CO₂.

In order to improve the performance of compressors and expanders, multiple stages are often employed. For example, in the calculations used in FIG. 20 it was assumed that the CO₂ was pressurized up to 900 psia from the starting pressure; this would be a one-stage process. For the purpose of the simulation, multiple expander or compressor units are modeled in series with heat exchangers to add/remove heat, as needed. FIG. 21 shows the variation in power input required to a compressor when it is run with 1-3 stages.

For the two-stage process, the first stage pressurized the 80° F. working fluid from 200-425 psia; the compression caused the fluid to warm, so a heat exchanger is used to reduce the temperature to 80° F. Then the second stage is run to pressurize from 425-900 psia.

For the three-stage process, the first stage pressurized the 80° F. working fluid from 200-330 psia; the compression caused the fluid to warm, so a heat exchanger is used to reduce the temperature to 80° F. Then the second stage is run to pressurize from 330-550 psia. Again, the compression heated working fluid is cooled to 80° F. and then enters the third stage where it achieves a final pressure of 900 psia.

As can be seen in FIG. 21, the additional stages reduce the power input required to pressurize the CO₂ working fluid. The difference is more significant between moving from one to two stages than from going two to three stages.

Of particular interest in evaluating the process will be the percentage of the recharge power that can be delivered in discharge mode; this will be referred to as the Round Trip Efficiency (RTE). The minimum acceptable value for this process is 0.6 (60%). FIG. 22 shows the calculated RTE for a system operating between 200-900 psia.

One method to improve power output is to pressurize the liquid CO₂ with a standard pump when it leaves the storage tank, and then add heat to move the working fluid into a supercritical state. This approach works because the power required to pressurize a liquid is significantly lower than the power output that can be gained from the expander (assuming a heat source is available, of course). FIG. 23 shows the improvement in RTE when the working fluid is delivered to the expander at 1400 psia.

Up to this point, the sorbent has not been considered in the analysis. All of the above calculations look at CO₂, and the power generated or consumed during discharge or recharge steps. The choice of sorbent is important for the system design. Of particular interest for the preceding analysis is the heat of solution. It has been assumed that the energy needed to heat the working fluid is available. One sorbent of interest is monoethanolamine (MEA). It has a high heat of solution with CO₂. Using the CHEMCAD AMINE model, it is possible to calculate the temperature of CO₂/MEA mixed solutions. One simulation looked at mixing 100% pure MEA with CO₂, and it was found that ˜17 wt % CO₂ was dissolved and the final solution temperature achieved 330° F. Using this heated sorbent as the heat supply for the CO₂ heat exchanger prior to the expander, we found that it was possible to heat the CO₂ to 280° F. in two expansion stages. The outgoing sorbent stream still retained a significant amount of heat, as the outlet temperature was ˜290° F. after heating the CO₂.

In order to achieve a high sorbent temperature, the MEA sorbent must dissolve a significant amount of CO₂. FIG. 18 shows the variation of temperature in MEA when CO₂ is added. To achieve high temperature (over 300° F.), the MEA must dissolve over 14 wt % CO₂. That means that significant CO₂ desorption must occur during the recharge step so the MEA will have the capacity to take up that much working fluid during the discharge step.

Example 4: Process Simulation No. 2

Another exemplary process was simulated using the software package described above. The following assumptions were made: 1) All streams can be heated or cooled to 80° F. from the atmosphere, whether heating or cooling. All phase change energy is supplied from the atmosphere. Energy to run the air blowers is neglected. 2) Working fluid liquid inlet condition is set at 70° F., where the fluid is a liquid at its vapor pressure. 3) Pressure is set between 100-856 psia and 200-856 psia. 4) Piston work is calculated as PdV. A simple curve fit of Pressure to Volume information was used for the integration. 5) Piston heat is calculated as TdS. 6) Assumed inefficiencies remained the same as with isentropic process—85% for expansion, 75% for compression. Lost energy is not accounted for in the simulation. 7) RTE is calculated as the power produced during piston expansion divided by the power required by the piston compression.

A schematic of the process used for the simulation is shown in FIGS. 1 and 2 for recharge and discharge, respectively. Process conditions and the resulting RTE are shown in Table 3, below. A CO₂ model was used to model the working fluid for the simulation.

TABLE 3 Discharge Sorption T = 160 F. Streams Unit Ops T (F.) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source 1 70 856 A +68.5 Air 2 80 856 B +28.1 System 3 150 856 C 35.2 −55.0 Exp. Cooling 4 150 200 D +55.0 System 5 160 200 E +2.4 System Recharge Desorption T = 60 F. Unit Ops T (F) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source 1 70 200 A −61.3 Air 2 70 856 B 47.6 +56.2 Comp Heat 3 70 856 C −56.2 System H^(ads) 85.5 kJ/sec 8.3 kJ/mol RTE 0.74

Discharge Sorption T = 160 F. Streams Unit Ops T (F.) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source 1 70 856 A +68.5 Air 2 80 856 B +28.1 System 3 150 856 C 54.5 −81.3 Exp. Cooling 4 150 100 D +81.3 System 5 160 100 E +2.3 System Recharge Desorption T = 60 F. Unit Ops T (F.) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source 1 70 100 A −61.3 Air 2 70 856 B 78.2 +83.0 Comp Heat 3 70 856 C −83.0 System H^(ads) 111.7 kJ/sec 10.8 kJ/mol RTE 0.70

To balance a system, such as the system described in this example or the other embodiments described herein, calculation of the minimum heat and maximum temperature of the absorber may be useful. Two criteria should be met. The first is the minimum heat of reaction required for the absorber. This is calculated by dividing the amount of energy required to reverse the chemical reaction of the working fluid with the absorber (the ‘B’ unit op column Q in the recharge cycle above) by the number of moles of working fluid needed to create a given amount of energy, which in this model is set at 1 #/sec. Thus, for CO₂ in this case is 10.32 moles.

So in the example above Q=56.2 kJ this divided by 10.32 moles=5.45 kJ/mole as a minimum reaction energy (delta G) for each mole of working fluid that reacts with each mole of absorber. The order of magnitude of this energy is actually very low compared to most chemical reactions. While it is good to have a delta G larger than the minimum it also needs to be reversible at a temperature that is available from the heat of compression. In general the higher the delta G the higher the temperature (and or pressure differential) that will be required to reverse the reaction. There is no exact formula that relates delta G to the temperature so each system has to be considered to make sure that it is reversible. Zeolites and activated carbons have delta G values of about 5 to about 20 kJ/mole for CO₂ and NH₃ working fluids. Another example is water and CO₂ going to HCO₃ ⁻, which has a delta G of about 12 kJ/mole. Many of these compounds can easily be desorbed by allowing the pressure to decrease on them.

In the case of a solid absorbent, a secondary heat transfer loop using an inert heat transfer liquid may also be used. Heat exchange could also be accomplished by injecting an inert heat exchange fluid (such as silicone oil) into the expander and/or compressor as opposed to the external heat exchangers discussed herein.

Example 5: Process Simulation No. 3

Another exemplary process was simulated using the computer software package described above. The following assumptions were made: 1) All streams can be heated or cooled to 80° F. from the atmosphere, whether heating or cooling. All phase change energy is supplied from the atmosphere. Energy to run the air blowers is neglected. 2) Working fluid (CO₂) liquid inlet condition is set at 70° F., where the fluid is a liquid at its vapor pressure. 3) Pressure is set between 200-856 psia. 4) Desorption conditions not accounted for—assumed to happen at any T, P set. No pressure or temperature swing has been included. 5) Work is calculated as isentropic. 6) Assumed inefficiencies based mechanical losses (BNI)—98% for expansion, 96% for compression. Lost energy is not accounted for in the simulation. 7) RTE is calculated as the power produced during piston expansion divided by the power required by the piston compression.

A schematic of the process used for the simulation is shown in FIGS. 3 and 4 for recharge and discharge, respectively. Process conditions and the resulting RTE are shown in Table 4, below. A CO₂ model was used to model the working fluid for the simulation.

TABLE 4 Carbon Dioxide - Isentropic, Single Stage. Discharge Sorption T = 210 F. Streams Unit Ops T (F.) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source 1 70 856 A +68.5 Air 2 80 856 B 31.0 3 150 856 C +17.7 Air 4 4.1 200 D +28.5 System 5 80 200 E +2.4 System 6 200 200 F +43.8 System Recharge Desorption T = 70 F. Unit Ops T (F.) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source 1 70 20 A −68.6 Air 2 286 856 B 40.7 3 80 856 C 4 70 856 D −68.9 System H^(ads) 68.9 kJ/sec 6.7 kJ/mol Heat from Absorber RTE 0.76

Carbon Dioxide—Isentropic, Two-Stage Expansion/Three-Stage Compression

Discharge Sorption T = 210 F. Streams Unit Ops T (F.) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source 1 70 856 A +68.5 Air 2 80 856 B 35.8 System 3 150 856 C +17.7 Air 4 102.5 200 D +28.5 System 5 80 200 E +2.4 System 6 200 200 F +43.8 System Recharge Desorption T = 70 F. Unit Ops T (F.) P (psi) W (kJ/sec) Q (kJ/sec) Heat Source 1 70 200 A −68.7 Air 2 135.8 856 B 39.5 −38.0 System 3 80 856 C 4 70 856 D −23.2 System H^(ads) 79.6 kJ/sec 7.7 kJ/mol Heat from absorber RTE 0.906

Example 6: Use of Air as Working Fluid and Half-Systems

One issue with conventional compressed air energy storage is the low energy density of the compressed gas. However, zeolite type absorbents will absorb air and have acceptable delta G values. If air were to be compressed into an insulated tank of zeolites, and then simply discharged to the atmosphere (no absorption on discharge) this would increase both the RTE of compressed air energy storage as well as the energy density.

This would operate conceptually as a half-system with only a single storage tank and that is not a closed cycle. However, it is an improvement over ordinary CAES. Both the heat of compression and the absorption energy will be stored and available for discharge. Although activated carbon also absorbs air, there should be a warning that high pressure air could ignite certain carbons and this would be a limit on those particular absorbents.

Example 7: Three-Loop Carbon Dioxide and Aqueous Ammonia System

The absorption of carbon dioxide in aqueous ammonia solution leads to a number of products including ammonium carbamate, bicarbonate, and carbonate. The ratio of these reaction products are a function of the carbon dioxide loading, solution pH, and the concentration of ammonia in the aqueous media.

Simplified chemical equations representing these reactions include:

NH₂COONH_(4(q))+H₂O↔NH₄HCO_(3(aq))+NH_(3(aq)) ΔH_(rx)=8.06 kJ/mol  (9)

2NH₄HCO_(3(aq))↔(NH₄)₂CO_(3(aq))+CO_(2(g))+H₂O ΔH_(rx)=26.88 kJ/mol  (10)

NH₄HCO_(3(aq))↔NH_(3(aq))+CO_(2(g))+H₂O ΔH_(rx)=64.26 kJ/mol  (11)

NH₂COONH_(4(aq))↔2NH_(3(aq))+CO_(2(g)) ΔH_(rx)=72.32 kJ/mol  (12)

(NH₄)₂CO_(3(aq))↔2NH_(3(aq))+CO_(2(g))+H₂O ΔH_(rx)=101.22 kJ/mol  (13)

The schematic flow diagram for the process is shown in FIG. 13.

The operating parameters for the initial feasibility evaluation are:

1) Absorption vessel conditions are 150° F. and 257 psi (˜66° C. and 1.77 Mpa);

2) Desorption vessel conditions are 180° F. and 257 psi (˜82° C.);

3) Ammonia concentration level of 36% was maintained;

4) Total flow rate of working fluid equal to 142.6 kg/s;

5) Expansion efficiency: 88%;

6) Compressor efficiency: 84%;

7) Heat exchanger efficiency: 2%;

8) The molar ratios of carbon dioxide to ammonia in solution are between 0.35 to 0.60;

9) The reversible heat of reaction: 80 kJ/mol; and

10) Thermodynamic and transport properties estimated with using the National Institute of Standards and Technology (NIST) standard reference program.

All state functions, for each location, as shown in FIG. 13 are shown in Table 5.

TABLE 5 Physical parameters data at various locations. Temperature Pressure Density Enthalpy Entropy Location³ (^(°) K) (Mpa) (kg/m³) (kJ/kg) (kJ/kg ^(°) K) 901 333.15 6.63 143.66 476.09 1.9083 903 333.15 3.76 69.441 506.26 2.0852 904 299.82 2.3442 47.202 484.33 2.0935 905 333.15 2.32 40.213 518.9 2.2043 906 298.71 1.77 34.596 489.59 2.1581 915 305.37 2.28 44.562 490.84 2.1193 916 333.71 3.17 56.84 512.2 2.1311 917 305.37 3.14 64.921 481.07 2.0351 918 333.15 4.316 81.984 500.96 2.0469 919 305.37 4.275 96.472 466.34 1.9401 920 334.26 5.9 120.76 486.74 1.9568 921 358.71 2.31 36.386 544.63 2.2795 934 333.15 1.74 29.28 523.73 2.2703   934(l)* 333.15 1.74 937 333.15 1.77 30.01 523.41 2.2653 940 339.93 6.63 136.34 486.23 1.9384 941 355.37 1.73 27.09 545.31 2.333 942 352.59 1.73 27.339 542.61 2.3254   943(l)* 330.37 1.77   945(l)* 355.37 1.73   946(l)* 352.59 1.73 ³Locations are shown in FIG. 13. *Assuming that heat capacity (C_(p)) of the solution (both rich and lean) containing CO₂/NH₃/H₂O is equal to 1 cal/g ^(°) C.

All calculations and thermodynamic state function are normalized to 1 kg of carbon dioxide of working fluid. The assumed value for heat capacity (C_(p)), for the carbon dioxide/ammonia/water solution is equal to 1 cal/g° C. The assumed density for the carbon dioxide/ammonia/water solution is equal to 1 g/cm³. The sensible heat requirements: 29.9 kJ/kg carbon dioxide and stripping heat is zero.

The value for each expansion and compression work is calculated as follows: E1 is calculated by referring to Table 5 above and FIG. 13, subtracting the H (enthalpy) of the noted output numbers corresponding to each device on the flow diagram (line 9, Table 5) from the H (enthalpy) of the input (line 1, Table 5). Thus, the value for E1 is 451.7−476.09=24.39. Similarly, the values for multi-stage expanders (E1, E2 and E3) and multi-stage compressors are shown in Tables 6 and 7.

TABLE 6 Multi-Stage Expanders. Expansion Heat Stages⁴ Work, kJ/kg CO₂ Exchangers Q kJ/kg CO₂ E1 −24.39 H_(x)1 54.56 E2 −21.93 H_(x)2 34.57 E3 −29.31 H_(x)3 33.82 Total −75.65 122.95 ⁴Expansion stages E1, E2 and E3 are shown in FIG. 13.

TABLE 7 Multi-Stage Compressors. Compression Heat Stages³ Work, kJ/kg CO₂ Exchangers Q kJ/kg CO₂ C1 20.90 H_(x)4 −53.79 C2 21.36 H_(x)5 −31.13 C3 19.89 H_(x)6 −34.62 C4 20.40 C5 −.61 Total: 82.55 −119.54 ³ Compression stages C1, C2, C3, C4 and C5 are shown in FIG. 13.

Estimation of Sensible Heat:

The sensible heat is defined as the amount of energy required to raise the temperature of the solution to the temperature of regeneration, which while not recovered in this flow chart, may allow for partial recovery. Assuming 36% by weight of ammonia concentration in water and maintaining the molar ratio of carbon dioxide to ammonia in the solution between 0.35 to 0.6 during absorption and desorption cycle, the reaction heat is:

(Q _(absorption) +Q _(desorption))/2=(122.95+119.54)/2=121.3 kJ/kg CO₂

Since the total ΔQ for desorption and absorption is essentially equal.

Accepting reaction heat 80 kJ/mol, as reported in the literature

80×[(1000×0.36)(0.6−0.35)/17]=424 kJ/kg of solution

The ΔT is the temperature difference between stream 43 and reboiler 180-135° F.=25° C.

-   -   Sensible (Q_(sensible)) heat is equal to

Q _(sensible)=(121.3×25×4.18)/424=29.9 kJ/kg CO₂

The System Efficiency:

Efficiency (RTE)=[(Work out)/(Work in+Sensible Heat)]×100

RTE=[75.65/(82.55+29.9)]×100=67.2%

Example 8: Process Simulation No. 4

The system illustrated in FIG. 15 was simulated using ASPEN modeling software. This simulation is independent of the absorbent and employs CO₂ as the working fluid.

This simulation calculates the thermodynamic efficiency of CO₂ working fluid as it completes a full charge-discharge cycle. Note that this simulation does not show a specific absorption reaction. It assumes that heat is put into a given reaction during charging/compression and withdrawn from the reverse of that reaction during the discharge/expansion thru the heat exchangers. The data generated in this simulation is presented in Tables 8-15, below.

TABLE 8 Expander Efficiency: 85%, Compressor Effic.: 84% Different Compressor Temperature Out. E30(P) = C10(P); C40(T, P) = E10(T, P); E30(T) NOT = C10(T) Final Heater Final Pr. Temp Temp Power Out Out Out MW E10 35.00 72.17 110 2.81 E10 in T/P: E20 15.00 51.20 100 4.38 115 deg C./61 bar E30 6.00 41.60 4.80 11.99 Final Cooler Final Pr. Temp Temp Power Out Out Out MW C10 14.94 100 69 6.90 C10 in T/P: C20 21.03 100 62 2.58 18 deg C./5.6 bar C30 35.46 110 63 3.82 C40 61.51 115 3.81 17.12 TRUE RTE 70.06

TABLE 9 Expander Efficiency: 85%, Compressor Effic.: 84% Different Compressor Temperature Out. E30(P) = C10(P); C40(T, P) = E10(T, P); E30(T) NOT = C10(T) Final Heater Final Pr. Temp Temp Power Out Out Out MW E10 35.00 72.17 110 2.81 E10 in T/P: E20 15.00 51.20 100 4.38 115 deg C./61 bar E30 6.00 41.60 4.80 11.99 Final Cooler Final Pr. Temp Temp Power Out Out Out MW C10 13.80 103 69 6.38 C10 in T/P: C20 21.02 103 62 3.17 28 deg C./5.7 bar C30 35.44 110 63 3.82 C40 61.47 115 3.81 17.19 TRUE RTE 69.78

TABLE 10 Expander Efficiency: 85%, Compressor Effic.: 84% Different Compressor Temperature Out. E30(P) = C10(P); C40(T, P) = E10(T, P); E30(T) NOT = C10(T) Final Heater Final Pr. Temp Temp Power Out Out Out MW E10 35.00 77.01 120 2.87 E10 in T/P: E20 15.00 60.49 105 4.53 120 deg C./61 bar E30 6.00 46.12 4.88 12.28 Final Cooler Final Pr. Temp Temp Power Out Out Out MW C10 12.25 101 64 5.48 C10 in T/P: C20 19.43 104.5 62 3.49 37 deg C./5.8 bar C30 33.89 112 61 4.10 C40 61.39 117 4.12 17.20 TRUE RTE 71.42

TABLE 11 Expander Efficiency: 85%, Compressor Effic.: 84% Different Compressor Temperature Out. E30(P) = C10(P); C40(T, P) = E10(T, P); E30(T) NOT = C10(T) Final Heater Final Pr. Temp Temp Power Out Out Out MW E10 35.00 72.17 110 2.81 E10 in T/P: E20 15.00 51.20 100 4.38 115 deg C./61 bar E30 6.00 41.60 4.80 11.99 Final Cooler Final Pr. Temp Temp Power Out Out Out MW C10 12.70 102 69 5.73 C10 in T/P: C20 20.01 105 62 3.45 35 deg C./5.8 bar C30 34.13 111 63 3.93 C40 61.20 116 4.04 17.15 TRUE RTE 69.94

TABLE 12 Expander Efficiency: 85%, Compressor Effic.: 84% Different Compressor Temperature Out. E30(P) = C10(P); C40(T, P) = E10(T, P); E30(T) NOT = C10(T) Final Heater Final Pr. Temp Temp Power Out Out Out MW E10 35.00 77.01 120 2.87 E10 in T/P: E20 15.00 60.49 105 4.53 120 deg C./61 bar E30 6.00 46.12 4.88 12.28 Final Cooler Final Pr. Temp Temp Power Out Out Out MW C10 12.48 102 64 5.58 C10 in T/P: C20 19.68 105 62 3.54 35 deg C./5.7 bar C30 33.57 111 61 4.10 C40 61.10 116 4.12 17.33 TRUE RTE 70.85

TABLE 13 Std Ideal Mass Liq Vol Vapor/ Molar Pressure Temp. Flow Flow Phase Enthalpy Location [bar] [C.] [kg/s] [m3/h] Fraction [kJ/kgmole] 1921 14.93721229 100 100 436.1865066 1 −391267.0048 1915 14.93721229 69 100 436.1865065 1 −392586.3377 1916 21.03372089 100 100 436.1865066 1 −391449.4834 1917 21.03372089 62 100 436.1865066 1 −393111.4838 1918 35.46339734 110 100 436.1865066 1 −391429.8615 1919 35.46339734 63 100 436.1865066 1 −393637.51 1940 61.51466519 115 100 436.1805066 1 −391959.8495 1934 5.6 18 100 436.1865066 1 −394303.7714 1909 35 72.1652056 100 436.1865066 1 −393181.8818 1903 35 110 100 436.1865066 1 −391416.2255 1904 15 51.19538871 100 436.1865066 1 −393342.6754 1905 15 100 100 436.1865066 1 −391268.8689 1906 6 41.60482521 100 436.1865066 1 −393382.2592 1941-2 61 22 100 436.1865066 0 −404047.2745 1900 61 115 100 436.1865066 1 −391944.4882 1941 61.51466519 22 100 436.1865066 0 −404077.447

TABLE 14 Hx40 Hx50 Hx60 Hx70 Duty [kJ/h] 10792163.03 13595187.4 18058597.24 9.9E+07 Pressure Drop 0 0 0 0 [kPa]

TABLE 15 C10 C20 C30 C40 Compressor Speed [rpm] Power [kW] 6900.221073 2583.190312 3821.02624 3812.02 Capacity (act feed vol flow) 34174.65632 14743.26663 9951.324512 5550.81 [ACT_m3/h] Adiabatic Efficiency 84 84 84 84 Polytropic Efficiency 85.57271157 84.58712734 84.90616828 84.988 Compressor Volume [m3] 0 0 0 0 Delta T [C] 82 31 48 52 Delta P [kPa] 933.7212287 609.6508608 1442.967645 2605.13 Polytropic Head [m] 6021.124725 2228.127363 3308.252024 3303.64 Adiabatic Head [m] 5910.464533 2212.661675 3272.944422 3265.23 Dynamic Head [m] 6021.124725 2228.127363 3308.252024 3303.64 Polytropic Fluid Head [kJ/kg] 59.04706278 21.8504652 32.44286971 32.3976 Adiabatic Fluid Head [kJ/kg] 57.96185701 21.69879862 32.09662041 32.021 Dynamic Fluid Head [kJ/kg] 59.04706278 21.8504652 32.44286971 32.3976 Polytropic Head Factor 1.00068214 1.00002664 0.999848205 0.99913 Polytropic Exponent 1.327392038 1.328738561 1.333983706 1.36064 Isentropic Exponent 1.266002311 1.261753035 1.266416427 1.2885 Dynamic Delta P RC-Typical Design Speed RC-Volumetric Efficiency PD Number of Cylinders 0 0 0 0 PD Bore [m] PD Stroke [m] PD Piston Rod Diameter [m] PD Const Volmetric Efficiency Loss [%] Transient Rotational Power 0 0 0 0 [kW] Friction Loss Power [kW] 0 0 0 0 Fluid Power [kW] 6900.221073 2583.190312 3821.02624 3812.02 Total Rotor Torque [N-m] Transient Rotational Torque [N-m] Friction Loss Torque [N-m] Fluid Torque [N-m] Duty [kJ/h] 24840795.86 9299485.123 13755694.46 1.4E+07

OTHER EMBODIMENTS

All publications and patents referred to in this disclosure are incorporated herein by reference to the same extent as if each individual publication or patent application were specifically and individually indicated to be incorporated by reference. Should the meaning of the terms in any of the patents or publications incorporated by reference conflict with the meaning of the terms used in this disclosure, the meaning of the terms in this disclosure are intended to be controlling. Furthermore, the foregoing discussion discloses and describes merely example embodiments of the present invention. One skilled in the art will readily recognize from such discussion and from the accompanying drawings and claims, that various changes, modifications and variations can be made therein without departing from the spirit and scope of the invention as defined in the following claims. 

1. A method for storing energy comprising: providing an absorbent reservoir containing a working fluid that is chemically absorbed by an absorbent; desorbing the working fluid from the absorbent in an endothermic process; and condensing the working fluid in an exothermic process and transferring the condensed working fluid to a working fluid reservoir under pressure; wherein at least some of the heat generated during the condensing step is recycled to drive the desorbing step.
 2. The method of claim 1, wherein the working fluid comprises carbon dioxide, ammonia, nitrous oxide, air, or water.
 3. The method of claim 2, wherein the working fluid comprises carbon dioxide or ammonia.
 4. The method of claim 3, wherein the absorbent comprises an organic amine, an inorganic base, an activated carbon, silica gel, a zeolite, a metal organic framework, or any combination thereof.
 5. The method of claim 4, wherein the absorbent comprises an organic amine selected from monoethanolamine, piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, diethylenetriamine, or any combination thereof.
 6. The method of claim 2, wherein the working fluid comprises ammonia.
 7. The method of claim 6, wherein the absorbent comprises a metal halide salt, a mild acid, water, activated carbon, silica gel, a zeolite, or metal organic framework.
 8. The method of claim 2, wherein the working fluid comprises nitrous oxide.
 9. The method of claim 8, wherein the absorbent comprises a food oil, silicone oil, activated carbon, silica gel, zeolite, or metal organic framework.
 10. The method of claim 1, wherein the heat generated from the condensing step is recycled to drive the desorbing step using a heat exchanger.
 11. The method of claim 1, further comprising compressing the working fluid using a reversible turbine.
 12. The method of claim 1, further comprising compressing the working fluid and storing the working fluid in the working fluid reservoir in a liquid state, a critical state, or a trans-critical state.
 13. The method of claim 1, wherein the working fluid is compressed to and stored at a pressure of from about 1 bar to about 100 bar.
 14. The method of claim 11, further comprising a second compression stage after the first compression.
 15. The method of claim 1, wherein the working fluid is expanded to a pressure of from about 0.1 bar to 10 bar.
 16. The method of claim 1, wherein the working fluid is stored at ambient temperature.
 17. The method of claim 1, further comprising heating the working fluid prior to expansion using an outside heat source.
 18. A method of charging and discharging an energy storage system comprising: charging the system comprising: providing an absorbent storage tank containing a working fluid that is chemically absorbed by an absorbent; desorbing the working fluid from the absorbent in an endothermic process; condensing the working fluid in an exothermic process and transferring the condensed working fluid to a working fluid reservoir under pressure; and recycling heat generated during the condensing step to drive the desorbing step; and storing the working fluid in a working fluid reservoir under pressure; and discharging the system comprising: expanding the working fluid; chemically absorbing the working fluid with the absorbent in the absorbent storage tank in an exothermic process; recycling heat generated during the absorption reaction to drive the expanding step; and storing the absorbent and the absorbed working fluid in the absorbent storage tank.
 19. The method of claim 18, wherein the working fluid comprises carbon dioxide, ammonia, nitrous oxide, air, or water.
 20. The method of claim 19, wherein the working fluid comprises carbon dioxide.
 21. The method of claim 20, wherein the absorbent comprises an organic amine, inorganic base, activated carbon, silica gel, zeolite, or metal organic framework.
 22. The method of claim 21, wherein the absorbent comprises an organic amine selected from monoethanolamine, piperazine, ammonia, morpholine, diethanolamine, diglycolamine, diisopropanolamine, triethanolamine, dibutylamine, methyl-diethanolamine, or diethylenetriamine.
 23. The method of claim 19, wherein the working fluid comprises ammonia.
 24. The method of claim 23, wherein the absorbent comprises a metal halide salt, mild acid, water, activated carbon, silica gel, zeolite, or metal organic framework.
 25. The method of claim 19, wherein the working fluid comprises nitrous oxide.
 26. The method of claim 25, wherein the absorbent comprises a food oil, silicone oil, activated carbon, silica gel, zeolite, or metal organic framework.
 27. The method of claim 18, wherein the heat generated during the condensing step is recycled drive the desorbing step using a heat exchanger.
 28. The method of claim 18, wherein the working fluid is compressed by a reversible turbine.
 29. The method of claim 18, further comprising compressing the working fluid and storing the working fluid in the working fluid reservoir in a liquid state, a critical state, or a trans-critical state.
 30. The method of claim 18, wherein the working fluid is compressed to and stored at a pressure of from about 1 bar to about 100 bar.
 31. The method of claim 29, wherein the compressing step comprises a two-stage compression process.
 32. The method of claim 18, wherein the working fluid is expanded to a pressure of from about 0.1 bar to 10 bar.
 33. The method of claim 18, wherein the working fluid is stored at ambient temperature.
 34. The method of claim 18, further comprising heating the working fluid prior to expansion using an external heat source.
 35. The method of claim 18, further comprising directing the flow of the working fluid a first direction during charging, and reversing the flow of the direction of the working fluid during discharging. 36.-60. (canceled) 